Water-soluble arylazodiarylamine dyestuffs and process of making same



Patente d Nov. 5, 1929 UNITED STATES PATENT OFFICE GERMANY, ASSIGNORS TO GENERAL ANILINE. WORKS,

CORPORATION OF DELAWARE 1110., on NEW YORK, N. Y., A

WATER-SOLUBLE ARYLAZODIARYLAMINE DYESTUFFS AND PROCESS OF MA'kING SAME No Drawing. Application filed August 13, 1927, Serial No. 212,842, and in Germany August 21, 1926.

Our present invention relates to new watersoluble arylazodiarylamine dyestufis and a process of preparing them.

We have found that valuable arylazodiarylamine dyestufis of the general formula:

- -zene and/or naphthalene series with nitro aryl compounds containing at least one exchangeable nuclear halogen atom and at least one sulfo cup or carboxyl group.

The ammoazo dyestufi used in the said process may belong either to the benzene or to the naphthalene series. It may however contain both a benzene nucleus and a naphthalene nucleus, and the amino grou which is acted upon by the condensation with the sulfonated or carboxylated nitrohalogenaryl,

may be situated in either the benzene or in the naphthalene nucleus. Furthermore, according to the purpose for which they are to be used and according to the degree of solubility of the finished dyestufis, the aminoazo dyestuffs used for the condensation may contain one or several solubilizing groups, such as a carboxyl group, a sulfo group or the like or no such gfiiup.

The sulfonated. or carboxylated nitro aryl compounds containing at least one exchangeable nuclear halogen, applicable in our new process may also belong either to the benzene They may, moreover,

sev-

or naphthalene series. contain one or several nitro groups or eral sulfo groups or carboxyl groups.

sides, sulfo grou s and carboxyl groups may The dyestuflt's obtalnbe present toget er. able by our new process not only dye animal fibe s but those that do not contain'more tha' one sulfo group are also particularly suitable for the dyeing of esters and ethers of cellulose and are, moreover, remarkable by the fact that they are not phototrope.

The condensation is in most cases carried caused to act' upon "preferably .under out in the presence of boiling water, preferably also in presence of an acid-binding agent, such as sodium acetate, chalk or the llke. In those cases in which the halogen can be exchanged only with difliculty, for instance in-the mononitrohalogenarylsulfonic ac ds ,or mononitrohalogenarylcarboxylic aclds, the application of: a pressure of about 6-12 atmospheres has proved to be advantageous in our new process.

The following examples serve to illustrate our invention, but they are not intended to limit it thereto, the parts being parts by weight: I

1. 197 parts of p-aminoazobenzene and 320,5 parts of potassium 1-chloro-2.6-dinitro benzenel-sulfonate are heated for several hours to boiling in water to which 118 parts of crystallized sodium acetate has been added. The dyestufi thus obtained has the following formula:

It crystallizes from water as a potassium salt in the form of reddish-yellow crystals and is remarkable for theexcellent properties of. the dyl 'eings they yield on acetyl cellulose.

2. f molecular proportions of p-aminoazobenzene-monosulfonic acid' and potassium l-chloro-2.6-dinitrobenzenc 4 sulfonate are each other,in, a manner similar to that set forth in Example 1, a dyestuff is obtained which gives on wool in- {ense dyeings, but does not dye acetyl celluose.

3. If n'itrobenzenel-sulfonic acid and amlnoazo benzol are caused to act upon each other for 6-8 hours at a temperature of about 120 C. in presence of water and 200 parts'of chalk,

atmospheres, a dyestuff is obtained which dyes animal fibers as well as acetate silk a yellow shade.

When the nitrochlorobenzenesul-fonic acids used in Examples 1 to 3' are replaced by nitrohalogenarylcarboxylic acidg dyestuffs of molecularproportions of 1-chloro-2- a pressure of about 6-12 A quite similar properties are obtained. Thus, for instance by causing molecular proportions of l-chloro-Q.6-dinitrobenzene-4-carboxylic acid and aminoazobenzene to act upon each other, a brownish-red dyestufi is obtained which dyes wool a reddish-yellow tint and yields on acetate silk an intense goldenyellow dyeing.

We claim:

1. A rocess for preparing water-soluble arylazo iarylamine dyestuffs, which consists in condensing a monoaminoazo dyestufi the aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one acid group.

2. A process for preparing water-soluble arylazodiarylamine dyestufl's, which consists in condensing a monoaminoazo dyestufi' the aryl nuclei of which belong. to the group consisting of benzene and naphthalene nuclei with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one sulfo group.

3. A rocess for reparing water-soluble arylazo iarylamine yestufis, which consists in condensing a monoaminoazo dyestuif the aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei in the presence of boiling water and an acidbinding agent with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one acid group.

4. A rocess for preparing water-soluble arylazo iarylamine dyestufis, which consists in condensing a monoaminoazo dyestufi the aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei in the presence of boilin water and of an acid-binding agent wit nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one sulfo group.

5. A rocess for reparing water-soluble arylazo iarylarnine yestufis, which consists in condensing a monoaminoazo dyestufi the aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei in the presence of boiling water and sodium acetate, with nitroaryl compounds containing at least one exchangeable nuclear halogen atom Aand at least one acid group. i

6. arylazo iarylamine dyestuffs, which consists in condensin a monoaminoazo dyestufl the aryl nuclei 0 which belong to the group consisting of benzene and naphthalene nuclei in the presence of boiling water and sodium acetate with nitroaryl compounds" containing at least one exchangeable nuclear halogen atom and at least one sulfo group.

7. A rocess for preparing water-soluble arylazo iarylamine dyestuffs, which consists in condensing a monoaminoazo dyestufi the group.

rocess for preparing water-soluble aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei in the presence of boiling water and an acidbinding agent and under a pressure of about 6-12 atmospheres, with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one acid group.

8. A process for preparing water-soluble arylazodiarylamine dyestufis, which consists in condensing a monoaminoazo dyestufl' the aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei in the presence of boiling water and of an acid-binding agent and under a pressure of about 612 atmospheres, with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one sulfo 9. A process for preparing water-soluble arylazodiarylamine dyestuffs, which consists in condensing a monoaminoazo dyestufi the aryl nuclei of which belong to the group consisting of benzene and naphthalene nuclei in the presence of boiling water and sodium acetate and under a pressure of about 6-12 atmospheres, with nitroarfil compounds containing at least one exc angeable nuclear halogen atom and at least one acid group.

10. A process for preparing water-soluble arylazodiarylamine dyestufis, which consists in condensing a monoaminoazo dyestufi the aryl nuclei of which belong to the .group consisting of benzene and naphthalene nuclei in the presence of boiling water and sodium acetate and under a pressure of about 6-12 atmospheres, with nitroaryl compounds con-. taining at least one exchangeable nuclear halogen atom and at least one sulfo group.

11. A process for preparin water-soluble arylazodiarylamine dyestu s, which consists in condensing aminoazobenzene in the presence of boiling, water and an acid-bindlng agent with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one acid group.

12. A process for preparin water-soluble arylazodiarylamine dyestu s, which consists in condensing aminoazobenzene in the presence of boiling water and of an acidbinding agent with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one sulfo group.

13. A process for preparing water-soluble arylazodiarylamine dyestufis, which consists in condensing aminoazobenzene, in the presence of boiling water and sodium acetate, with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and at least one acid group. I

14. A process -for preparing water-soluble arylazodiarylamine dyestufi's, which consists in condensing aminoazobenzene, in the presence of boiling water and sodium acetate, with nitroaryl compounds containing at least one exchangeable nuclear halogen atom and In testimony whereof, we aflix our sigat least one sulfo group. natures.

15. A process for preparing a water-solu- INZ E10. f" DE. ble arylazodiarylamme dyestufi of the fol- ,ERICH FISCR. lowing formula: OLF SIEGLI.

which consists in condensin para-aminoazobenzene with potassium l-c lore-2.6 dinitrobenzene-4-sulfonate in the presence of boiling water and sodium acetate. A

15 16. As new products, a lazodiarylamine w dyestuffs of the following ormula:

wherein aryl stands for an aryl nucleus of the group consisting of benzene and naphthalene nuclei which may be substituted or not and X stands for COO-alkali or SO O-alkali, said s5 dyestufis being water-soluble and yielding intense dyeings which on acetate silk are not phototrope.

17. As new products, arylazodiarylamine dyestuffs of the following formula:

wherein aryl stands for an aryl nucleus of the 7 group consisting of benzene and naphthalene v nuclei which may be substituted or not and X stands for COO-alkali or SO O-alkali, said dyestuffs being soluble in water and giving intense dyeings which on acetate silk 0 are not phototrope. 10s 18. As a new product, the dyestufi of the following formula:

wherein X stands vfor hydrogen or a nitro group, said dyestufi being soluble in water 60 and dyeing wool and acetyl cellulose yellow tint and its dyeing on acetate silk being non phototrope.

19. As a new product, the dyestufi' of the following formula:

" said dyestufi being soluble in water, crystallizing from water as reddish-yellow crystals and being distinguished by the excellent ,?properties of its dyeings on acet 1 cellulose l sand its dyeing on acetate silk ing nonphototrope. i

V Certificate of Correction v Patent 1 104 334 4 I Granted November 5, 1929, to

' HEINZ EIOHWEDE ET AL.

w it is hereby certified that error appears in the printed specification of the abovenumberedpatent requiring correction as follows: Page '3, llne 30, strike out the formula. and insert insteed and, that the said Letters Patent should be read with this correction therein that the same may conform to the record of the casein the Patent Ofiice.

Signedeud seeled thie Sth'day of December, A. D. 1929.

. M. J; MOOREQ. ti j a migs'iofler of Patents 

